CN107359339A - A kind of preparation method of the lithium sulfur battery anode material of porous carbon load phosphatization nickel material - Google Patents
A kind of preparation method of the lithium sulfur battery anode material of porous carbon load phosphatization nickel material Download PDFInfo
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- CN107359339A CN107359339A CN201710585395.XA CN201710585395A CN107359339A CN 107359339 A CN107359339 A CN 107359339A CN 201710585395 A CN201710585395 A CN 201710585395A CN 107359339 A CN107359339 A CN 107359339A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
A kind of preparation method of the lithium sulfur battery anode material of porous carbon load phosphatization nickel material, belongs to field of energy source materials.Methods described step is as follows：（1）Nickel salt and hypophosphites and distilled water are configured to dipping solution；（2）Dried after above-mentioned dipping solution is well mixed with porous carbon materials, obtain the porous carbon matrix precursor impregnated of solution；（3）Obtained porous carbon matrix precursor is calcined in inert atmosphere tube furnace, obtains porous carbon load phosphatization nickel material；（4）Obtained porous carbon load phosphatization nickel material is mixed with sublimed sulfur, cooled down after high-temperature calcination, obtains the lithium sulfur battery anode material of porous carbon load phosphatization nickel material.The material of the present invention is significantly improved to the load capacity of sulphur, nickel phosphide provides the catalytic site of high activity for chemical reaction, improve the electrochemical reaction activity of sulphur, and the chemical adsorption capacity for passing through nickel phosphide, the cycle life of material is significantly improved, material has been taken into account long circulation life and high-energy-density.
Description
Technical field
The invention belongs to field of energy source materials, and in particular to a kind of lithium-sulphur cell positive electrode of porous carbon load phosphatization nickel material
The preparation method of material.
Background technology
The ratio energy of lithium-sulfur cell is up to 2600Wh/kg in theory.This numerical value be 5 times of existing lithium ion battery with
On.Meanwhile the pollution of sulphur is small, it is cheap the features such as its application in the battery is widely paid close attention to and is studied by people.
But lithium-sulfur cell uses elemental sulfur that its electrical conductivity is low as positive electrode, the more lithium sulfides of electric discharge intermediate product are in the electrolytic solution
There is certain solubility, the features such as reactivity of unwinding is poor, limit its development always.Therefore above-mentioned weakness result in lithium sulphur electricity
The problems such as overall electro-chemical activity in cyclic process in pond is poor, capacitance loss is serious in cyclic process.Therefore greatly limit
Commercial application and the marketing of lithium-sulfur cell are made.
In order to solve the problems, such as that sulphur positive pole cycle life is short, reactive material is active poor, a variety of porous carbons are developed
Material is as sulfur-donor so as to limiting the generation of shuttle effect and improve the overall electrical conductivity of electrode.Carbon material possesses super by it
The advantages such as high-specific surface area, abundant pore structure, good electrochemicaUy inert are widely used in lithium-sulfur cell.But
Sulphur and its discharging product are fixed by way of physical absorption and can not be reached by carbon material nonpolar interface merely
Good effect.And polar material effectively can be discharged lithium-sulfur cell intermediate product Li by the effect of polar bond2Sn
(4≤n≤8) are fixed on the surface of carrier, are spread so as to limit it into electrolyte.Therefore a kind of porous carbon and polarity material are needed badly
Compound advanced composite material (ACM) is expected as sulfur-donor, the cycle life of raising electrode on the premise of electrode energy density is ensured.
The content of the invention
The invention aims to overcome present in prior art, positive pole cycle life is short, reactive material is active poor
The problem of, there is provided a kind of preparation method of the lithium sulfur battery anode material of porous carbon load nickel phosphide.This method is using molten
Liquid dipping porous carbon materials obtain the porous carbon matrix precursor impregnated of solution, and obtain porous carbon by subsequent calcining and cleaning
Load phosphatization nickel material.During inversion of phases, nickel phosphide has been evenly dispersed in the hole of porous carbon materials.
To achieve the above object, the technical scheme that the present invention takes is as follows：
A kind of preparation method of the lithium sulfur battery anode material of porous carbon load phosphatization nickel material, methods described include following step
Suddenly：
Step 1：By 10-1000mmol nickel salt, 10-1000mmol hypophosphites, 10-1000mL distilled water is added to
In be configured to solution, obtain dipping solution；
Step 2：The dipping solution that step 1 obtains is well mixed with 10-1000g porous carbon materials, dries, is impregnated
The porous carbon matrix precursor of solution；
Step 3：It is small that the porous carbon matrix precursor impregnated of solution that step 2 is obtained calcines 1-24 in inert atmosphere tube furnace
When, calcining heat is 130-500 DEG C, is then cleaned with distilled water, is dried, and obtains porous carbon load phosphatization nickel material；
Step 4：The porous carbon load phosphatization nickel material that step 3 is obtained is with sublimed sulfur according to 1:0.5-19 mass ratio mixes
Close, after grinding uniformly, at 120-250 DEG C, the small inert atmospheres at present of 5-24 are heated to melting and being subsequently cooled to room temperature, obtain more
The lithium sulfur battery anode material of hole carbon load phosphatization nickel material.
It is of the invention to be relative to the beneficial effect of prior art：
（1）The porous carbon materials that the present invention has loaded nickel phosphide have the intermediate product Li that discharges lithium-sulfur cell2Sn (4≤n≤8)
There is very strong chemical bonding effect, more lithium sulfides are adsorbed by chemical bond in charge and discharge process, so as to significantly inhibit the effect that shuttles
The generation answered；
（2）The porous carbon materials that the present invention has loaded nickel phosphide have obvious facilitation to the electrochemical reaction of sulphur, so as to increase
The electro-chemical activity and reaction depth of strong lithium-sulphur cell positive electrode；
（3）Porous carbon load phosphatization nickel material prepared by the present invention maintains the high-ratio surface of porous carbon materials in preparation process
The property of product and big pore volume, therefore in addition to improving electrochemical reaction activity, additionally it is possible to abundant storage sulphur place is provided.So as to
Enough the problem of effectively suppressing volumetric expansion during lithium-sulfur cell electric discharge.
Brief description of the drawings
Fig. 1 is that porous carbon prepared by the present invention loads scanning electron microscope (SEM) photograph of the phosphatization nickel material under the conditions of 50000 times of amplifications；
Fig. 2 is that porous carbon prepared by the present invention loads scanning electron microscope (SEM) photograph of the phosphatization nickel material under the conditions of 5000 times of amplifications；
Fig. 3 is the X-ray diffraction spectrogram that porous carbon prepared by the present invention loads phosphatization nickel material；
Fig. 4 is discharge cycles song of the lithium sulfur battery anode material in 0.2C that porous carbon prepared by the present invention loads phosphatization nickel material
Line chart.
Embodiment
Technical scheme is described further with reference to the accompanying drawings and examples, but is not limited thereto, it is all
It is technical solution of the present invention to be modified or equivalent substitution, without departing from the scope of technical solution of the present invention, all should contains
Cover among protection scope of the present invention.
Embodiment one：What present embodiment was recorded is that a kind of porous carbon is loading the lithium-sulfur cell of phosphatization nickel material just
The preparation method of pole material, the described method comprises the following steps：
Step 1：By 10-1000mmol nickel salt, 10-1000mmol hypophosphites, 10-1000mL distilled water is added to
In be configured to solution, obtain dipping solution；
Step 2：The dipping solution that step 1 obtains is well mixed with 10-1000g porous carbon materials, dries, is impregnated
The porous carbon matrix precursor of solution；
Step 3：It is small that the porous carbon matrix precursor impregnated of solution that step 2 is obtained calcines 1-24 in inert atmosphere tube furnace
When, calcining heat is 130-500 DEG C, is then cleaned with distilled water, is dried, and obtains porous carbon load phosphatization nickel material；
Step 4：The porous carbon load phosphatization nickel material that step 3 is obtained is with sublimed sulfur according to 1:0.5-19 mass ratio mixes
Close, after grinding uniformly, at 120-250 DEG C, the small inert atmospheres at present of 5-24 are heated to melting and being subsequently cooled to room temperature, obtain more
The lithium sulfur battery anode material of hole carbon load phosphatization nickel material.
Embodiment two：The lithium-sulphur cell positive electrode of porous carbon load phosphatization nickel material described in embodiment one
The preparation method of material, in step 1, described nickel salt is in nickel sulfate, nickel nitrate, nickel acetate, nickelous hypophosphite, nickel chloride
One kind, described hypophosphites are one kind in sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite.
Embodiment three：The lithium-sulphur cell positive electrode of porous carbon load phosphatization nickel material described in embodiment one
The preparation method of material, in step 2, described porous carbon materials be carbon black, acetylene black, Super_P, Ke Qinhei, graphene,
One kind in CNT, activated carbon, porous carbon.
Embodiment four：The lithium-sulphur cell positive electrode of porous carbon load phosphatization nickel material described in embodiment one
The preparation method of material, in step 3, filling gas is one kind in nitrogen, argon gas, helium in inert atmosphere tube furnace.
Embodiment 1：
（1）First by 10mmol nickel sulfate, 10mmol sodium hypophosphite, it is added in 10mL distilled water and is configured to solution,
Obtain dipping solution.
（2）By step（1）The dipping solution of acquisition is well mixed with 10g carbon black, and is obtained after drying impregnated of solution
Porous carbon matrix precursor.
（3）By step（2）The porous carbon matrix precursor impregnated of solution obtained is forged 130 DEG C in nitrogen atmosphere tube furnace
Burn 1 hour, and then cleaned with distilled water, dried, obtain porous carbon load phosphatization nickel material.
（4）By step（3）The porous carbon load phosphatization nickel material of acquisition is with sublimed sulfur according to 1:0.5 mass ratio mixing,
After grinding uniformly, at 120 DEG C, 5 small nitrogen atmospheres at present are heated to melting and being subsequently cooled to room temperature, obtain porous carbon load phosphorus
Change the lithium sulfur battery anode material of nickel material.
Embodiment 2：
（1）First by 200mmol nickelous hypophosphite, 500mmol potassium hypophosphite, it is added in 300mL distilled water and is configured to
Solution, obtain dipping solution.
（2）By step（1）The dipping solution of acquisition is well mixed with 1000g graphene, and obtained after drying impregnated of
The porous carbon matrix precursor of solution.
（3）By step（2）The porous carbon matrix precursor impregnated of solution obtained is forged 300 DEG C in helium atmosphere tube furnace
Burn 5 hours, and then cleaned with distilled water, dried, obtain porous carbon load phosphatization nickel material.Obtain as shown in Figure 1 and Figure 2
Porous carbon load phosphatization nickel material is the micron powder that more nano particle clusters form, and Fig. 3 is that X-ray diffraction spectrum figure is shown
Obvious the amorphous state diffraction maximum of carbon and the crystalline state diffraction maximum of nickel phosphide, wherein, 41 °, 45 °, 47 °, 54 ° of diffraction maximum it is right respectively
Answer nickel phosphide（111）、（201）、（210）、（300）Crystal face.
（4）By step（3）The porous carbon load phosphatization nickel material of acquisition is with sublimed sulfur according to 1:4 mass ratio mixing, grinds
After mill is uniform, at 180 DEG C, 18 small helium atmospheres at present are heated to melting and being subsequently cooled to room temperature, obtain porous carbon load phosphorus
Change the lithium sulfur battery anode material of nickel material.It is illustrated in figure 4 the lithium-sulfur cell of porous carbon load phosphatization nickel material of acquisition just
Cyclic curve figure of the pole material under 0.2C multiplying powers, it can be seen that battery still maintains 950 MAhs/g in 60 circulations
Specific capacity.
Embodiment 3：
（1）First by 1000mmol nickel chloride, 200mmol ammonium hypophosphite, it is added in 700mL distilled water and is configured to
Solution, obtain dipping solution.
（2）By step（1）The dipping solution of acquisition is well mixed with 200g activated carbon, and is obtained after drying impregnated of molten
The porous carbon matrix precursor of liquid.
（3）By step（2）The porous carbon matrix precursor impregnated of solution obtained is forged 180 DEG C in argon gas atmosphere tube furnace
Burn 10 hours, and then cleaned with distilled water, dried, obtain porous carbon load phosphatization nickel material.
（4）By step（3）The porous carbon load phosphatization nickel material of acquisition is with sublimed sulfur according to 1:9 mass ratio mixing, grinds
After mill is uniform, at 250 DEG C, 20 small argon gas atmospheres at present are heated to melting and being subsequently cooled to room temperature, obtain porous carbon load phosphorus
Change the lithium sulfur battery anode material of nickel material.
Embodiment 4：
（1）First by 100mmol nickel acetates, 1000mmol potassium hypophosphite, be added in 50mL distilled water be configured to it is molten
Liquid, obtain dipping solution.
（2）By step（1）The dipping solution of acquisition is well mixed with 100g Ke Qinhei, and is obtained after drying impregnated of molten
The porous carbon matrix precursor of liquid.
（3）By step（2）The porous carbon matrix precursor impregnated of solution obtained is forged 400 DEG C in nitrogen atmosphere tube furnace
Burn 24 hours, and then cleaned with distilled water, dried, obtain porous carbon load phosphatization nickel material.
（4）By step（3）The porous carbon load phosphatization nickel material of acquisition is with sublimed sulfur according to 1:2 mass ratio mixing, grinds
After mill is uniform, at 220 DEG C, 10 small nitrogen atmospheres at present are heated to melting and being subsequently cooled to room temperature, obtain porous carbon load phosphorus
Change the lithium sulfur battery anode material of nickel material.
Embodiment 5：
（1）First by 50mmol nickel nitrate, 100mmol ammonium hypophosphite, be added in 1000mL distilled water be configured to it is molten
Liquid, obtain dipping solution.
（2）By step（1）The dipping solution of acquisition is well mixed with 600g porous carbon, and is obtained after drying impregnated of molten
The porous carbon matrix precursor of liquid.
（3）By step（2）The porous carbon matrix precursor impregnated of solution obtained is forged 500 DEG C in helium atmosphere tube furnace
Burn 18 hours, and then cleaned with distilled water, dried, obtain porous carbon load phosphatization nickel material.
（4）By step（3）The porous carbon load phosphatization nickel material of acquisition is with sublimed sulfur according to 1:19 mass ratio mixing, grinds
After mill is uniform, at 150 DEG C, 14 small helium atmospheres at present are heated to melting and being subsequently cooled to room temperature, obtain porous carbon load phosphorus
Change the lithium sulfur battery anode material of nickel material.
Embodiment 6：
（1）First by 500mmol nickel acetate, 50mmol sodium hypophosphite, be added in 200mL distilled water be configured to it is molten
Liquid, obtain dipping solution.
（2）By step（1）The dipping solution of acquisition is well mixed with 50g Super_P, and is obtained after drying impregnated of molten
The porous carbon matrix precursor of liquid.
（3）By step（2）The porous carbon matrix precursor impregnated of solution obtained is forged 200 DEG C in argon gas atmosphere tube furnace
Burn 16 hours, and then cleaned with distilled water, dried, obtain porous carbon load phosphatization nickel material.
（4）By step（3）The porous carbon load phosphatization nickel material of acquisition is with sublimed sulfur according to 1:14 mass ratio mixing, grinds
After mill is uniform, at 160 DEG C, 12 small argon gas atmospheres at present are heated to melting and being subsequently cooled to room temperature, obtain porous carbon load phosphorus
Change the lithium sulfur battery anode material of nickel material.
Embodiment 7：
（1）First by 20mmol nickel chloride, 800mmol potassium hypophosphite, be added in 100mL distilled water be configured to it is molten
Liquid, obtain dipping solution.
（2）By step（1）The dipping solution of acquisition is well mixed with 300g acetylene black, and is obtained after drying impregnated of molten
The porous carbon matrix precursor of liquid.
（3）By step（2）The porous carbon matrix precursor impregnated of solution obtained is forged 130 DEG C in nitrogen atmosphere tube furnace
Burn 3 hours, and then cleaned with distilled water, dried, obtain porous carbon load phosphatization nickel material.
（4）By step（3）The porous carbon load phosphatization nickel material of acquisition is with sublimed sulfur according to 1：1 mass ratio mixing, grinds
After mill is uniform, at 200 DEG C, 24 small nitrogen atmospheres at present are heated to melting and being subsequently cooled to room temperature, obtain porous carbon load phosphorus
Change the lithium sulfur battery anode material of nickel material.
Embodiment 8：
（1）First by 800mmol nickelous hypophosphite, 20mmol sodium hypophosphite, be added in 20mL distilled water be configured to it is molten
Liquid, obtain dipping solution.
（2）By step（1）The dipping solution of acquisition is well mixed with 30g CNT, and obtained after drying impregnated of
The porous carbon matrix precursor of solution.
（3）By step（2）The porous carbon matrix precursor impregnated of solution obtained is forged 250 DEG C in argon gas atmosphere tube furnace
Burn 8 hours, and then cleaned with distilled water, dried, obtain porous carbon load phosphatization nickel material.
（4）By step（3）The porous carbon load phosphatization nickel material of acquisition is with sublimed sulfur according to 1:12 mass ratio mixing, grinds
After mill is uniform, at 210 DEG C, 8 small argon gas atmospheres at present are heated to melting and being subsequently cooled to room temperature, obtain porous carbon load phosphatization
The lithium sulfur battery anode material of nickel material.
Claims (4)
- A kind of 1. preparation method of the lithium sulfur battery anode material of porous carbon load phosphatization nickel material, it is characterised in that：The side Method comprises the following steps：Step 1：By 10-1000mmol nickel salt, 10-1000mmol hypophosphites, 10-1000mL distilled water is added to In be configured to solution, obtain dipping solution；Step 2：The dipping solution that step 1 obtains is well mixed with 10-1000g porous carbon materials, dries, is impregnated The porous carbon matrix precursor of solution；Step 3：It is small that the porous carbon matrix precursor impregnated of solution that step 2 is obtained calcines 1-24 in inert atmosphere tube furnace When, calcining heat is 130-500 DEG C, is then cleaned with distilled water, is dried, and obtains porous carbon load phosphatization nickel material；Step 4：The porous carbon load phosphatization nickel material that step 3 is obtained is with sublimed sulfur according to 1:0.5-19 mass ratio mixes Close, after grinding uniformly, at 120-250 DEG C, the small inert atmospheres at present of 5-24 are heated to melting and being subsequently cooled to room temperature, obtain more The lithium sulfur battery anode material of hole carbon load phosphatization nickel material.
- 2. the preparation method of the lithium sulfur battery anode material of porous carbon load phosphatization nickel material according to claim 1, its It is characterised by：In step 1, described nickel salt is nickel sulfate, one kind in nickel nitrate, nickel acetate, nickelous hypophosphite, nickel chloride, institute The hypophosphites stated is one kind in sodium hypophosphite, potassium hypophosphite, ammonium hypophosphite.
- 3. the preparation method of the lithium sulfur battery anode material of porous carbon load phosphatization nickel material according to claim 1, its It is characterised by：In step 2, described porous carbon materials are carbon black, acetylene black, Super_P, Ke Qinhei, graphene, carbon nanometer One kind in pipe, activated carbon, porous carbon.
- 4. the preparation method of the lithium sulfur battery anode material of porous carbon load phosphatization nickel material according to claim 1, its It is characterised by：In step 3, filling gas is one kind in nitrogen, argon gas, helium in inert atmosphere tube furnace.
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Cited By (10)
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| CN108511714A (en) * | 2018-03-27 | 2018-09-07 | 燕山大学 | A kind of transition metal phosphide-carbon composite and its preparation method and application |
| CN109524637A (en) * | 2018-09-30 | 2019-03-26 | 肇庆市华师大光电产业研究院 | A kind of porous self-supporting flexible electrode material of lithium-sulfur cell and preparation method thereof |
| CN109686933A (en) * | 2018-12-12 | 2019-04-26 | 电子科技大学 | It is a kind of using carbon cloth as the preparation method of the lithium-sulfur cell self-supporting positive electrode of substrate |
| CN110038613A (en) * | 2019-05-10 | 2019-07-23 | 安徽理工大学 | A kind of self-supporting Ferrious material phosphide/carbon composite and preparation method thereof, application |
| CN110444745A (en) * | 2019-07-22 | 2019-11-12 | 华中科技大学 | A kind of porous hollow carbon material of carried metal phosphide, its preparation and application |
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| CN111477873A (en) * | 2020-04-14 | 2020-07-31 | 山东大学 | Lithium-sulfur battery conductive agent based on nano transition metal phosphide/carbon composite material and preparation method and application thereof |
| CN112201782A (en) * | 2020-10-16 | 2021-01-08 | 西南大学 | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof |
| CN112206794A (en) * | 2020-10-16 | 2021-01-12 | 泰州九润环保科技有限公司 | Hydroxyapatite nanotube supported catalyst with limited length-diameter ratio and preparation method thereof |
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| CN108511714B (en) * | 2018-03-27 | 2020-05-12 | 燕山大学 | Transition metal phosphide-carbon composite material and preparation method and application thereof |
| CN108511714A (en) * | 2018-03-27 | 2018-09-07 | 燕山大学 | A kind of transition metal phosphide-carbon composite and its preparation method and application |
| CN109524637A (en) * | 2018-09-30 | 2019-03-26 | 肇庆市华师大光电产业研究院 | A kind of porous self-supporting flexible electrode material of lithium-sulfur cell and preparation method thereof |
| CN109686933A (en) * | 2018-12-12 | 2019-04-26 | 电子科技大学 | It is a kind of using carbon cloth as the preparation method of the lithium-sulfur cell self-supporting positive electrode of substrate |
| CN110038613A (en) * | 2019-05-10 | 2019-07-23 | 安徽理工大学 | A kind of self-supporting Ferrious material phosphide/carbon composite and preparation method thereof, application |
| CN110444745A (en) * | 2019-07-22 | 2019-11-12 | 华中科技大学 | A kind of porous hollow carbon material of carried metal phosphide, its preparation and application |
| CN110444745B (en) * | 2019-07-22 | 2021-10-15 | 华中科技大学 | Porous hollow carbon material loaded with metal phosphide, and preparation and application thereof |
| CN110660977A (en) * | 2019-08-23 | 2020-01-07 | 太原理工大学 | Lithium-sulfur electrochemical energy storage system and preparation method thereof |
| CN111477873A (en) * | 2020-04-14 | 2020-07-31 | 山东大学 | Lithium-sulfur battery conductive agent based on nano transition metal phosphide/carbon composite material and preparation method and application thereof |
| CN112201782A (en) * | 2020-10-16 | 2021-01-08 | 西南大学 | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof |
| CN112206794A (en) * | 2020-10-16 | 2021-01-12 | 泰州九润环保科技有限公司 | Hydroxyapatite nanotube supported catalyst with limited length-diameter ratio and preparation method thereof |
| CN112206794B (en) * | 2020-10-16 | 2021-12-07 | 泰州润瀚环境科技有限公司 | Hydroxyapatite nanotube supported catalyst with limited length-diameter ratio and preparation method thereof |
| CN114447331A (en) * | 2021-12-16 | 2022-05-06 | 山东大学苏州研究院 | Biomass carbon source-based lithium-sulfur battery positive electrode composite material and preparation method and application thereof |
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